Method for oxidation of xylene derivatives

ABSTRACT

Xylene derivatives, such as chloro-ortho-xylene, are oxidized in a solvent in the presence of at least one metal catalyst and optionally at least one promoter. The product comprises chlorophthalic acid or chlorophthalic anhydride.

This application claims priority of a Provisional Application, SerialNo. 60/167,266, filed Nov. 24, 1999.

BACKGROUND OF THE INVENTION

This invention relates to a method for oxidizing xylene derivatives.More particularly, the invention relates to a method for oxidizing asubstrate comprising at least one halo-ortho-xylene in the presence ofat least one metal catalyst, at least one solvent, and optionally atleast one promoter to provide a product comprising halo-phthalic acid orhalo-phthalic anhydride. In one key embodiment the invention relates toa method for producing a product comprising 4-chlorophthalic acid or4-chlorophthalic anhydride.

Methods for oxidizing ortho-xylene are known. For example, U.S. Pat. No.3,402,184 describes oxidation of ortho-xylene in acetic acid solvent inthe presence of a bromine promoter. U.S. Pat. Nos. 5,958,821, 5,981,420,and 6,020,522 describe oxidation of ortho-xylene in acetic acid solventin the presence of a hydroxyimide promoter. Methods for preparing4-chlorophthalic anhydride are also known. However, these methodstypically involve aromatization of a Diels-Alder adduct of chloropreneand a maleic anhydride as in U.S. Pat. No. 5,322,954, or chlorination ofphthalic acid as in Japanese patent applications 07258152 and 02129143.The latter chlorination process may produce polychlorinated biphenyls(PCBs). There is a need for a method for producing 4-chlorophthalicanhydride which does not involve handling toxic chloroprene or chlorinegas, and which does not produce PCBs.

SUMMARY OF THE INVENTION

In one embodiment the invention is a method for oxidizing a substratecomprising at least one halo-ortho-xylene which comprises combining thesubstrate in a solvent with at least one metal catalyst and heating inthe presence of an oxygen source to produce a product mixture.

In another embodiment the invention is a method for oxidizing asubstrate comprising 4-chloro-ortho-xylene which comprises combiningchloro-ortho-xylene in acetic acid solvent with at least one metalcatalyst which is a metal compound comprising cobalt, and heating in thepresence of an oxygen source to produce a product mixture comprising4-chlorophthalic acid or 4-chlorophthalic anhydride.

In still another embodiment the invention is a method for producing aproduct mixture comprising 4-chlorophthalic acid or 4-chlorophthalicanhydride which comprises oxidizing a substrate comprising4-chloro-ortho-xylene, optionally in the presence of chlorotoluic acid,which comprises the steps of

(i) combining substrate in acetic acid solvent with at least one metalcatalyst comprising cobalt, and optionally manganese, and heating in thepresence of an oxygen source to a temperature in a range of betweenabout 100° C. and about 230° C. at pressure in a range of between about1300 and about 8300 kilopascals, wherein the molar ratio of substrate tothe at least one metal catalyst is in a range of about 80-250:1; and

(ii) isolating product comprising 4-chlorophthalic acid or4-chlorophthalic anhydride.

DETAILED DESCRIPTION; PREFERRED EMBODIMENTS

In one embodiment the substrate comprising at least onehalo-ortho-xylene of the present invention preferably comprises amonohalo-ortho-xylene, more preferably 4-halo-ortho-xylene, mostpreferably 4-fluoro- or 4-chloro-ortho-xylene. In another embodiment thesubstrate comprises a mixture of 4-halo- and 3-halo-ortho-xylene,preferably a mixture of 4-fluoro- and 3-fluoro-ortho-xylene or a mixtureof 4-chloro- and 3-chloro-ortho-xylene. When 3-halo-ortho-xylene ispresent, it comprises about 0.001-15 molar percent, preferably about0.01-12 molar percent, and more preferably about 0.1-10 molar percent oftotal substrate.

In yet another embodiment the substrate comprises at least onehalo-ortho-xylene as described above, optionally in the presence of atleast one halotoluic acid, preferably at least one chlorotoluic acid(also known as chloro methylbenzoic acid), more preferably either (a)4-chloro-2-methyl benzoic acid or (b) 5-chloro-2-methylbenzoic acid or(c) a mixture thereof, and still more preferably a mixture of either orboth of (a) and (b) with either (d) 4-halo-ortho-xylene, or (e) amixture of 4-halo- and 3-halo-ortho-xylene. Halo-toluic acid may beeither added to the substrate or may be present as a consequence ofpartial oxidation of halo-ortho-xylene. As a consequence of partialoxidation the amount of halo-toluic acid in the substrate will vary withsuch factors as reaction temperature, time, and catalyst.

In still another embodiment the substrate comprises a mixture ofortho-xylene with halo-ortho-xylene, preferably either with (d)4-halo-ortho-xylene, or with (e) a mixture of 4-halo- and3-halo-ortho-xylene, or with at least one halotoluic acid, preferablychlorotoluic acid, or with a mixture of chlorotoluic acid with either(d) 4-halo-ortho-xylene, or (e) a mixture of 4-halo- and3-halo-ortho-xylene. When ortho-xylene is present, it comprises about0.001-10 molar percent and preferably about 0.01-1 molar percent oftotal substrate. An especially preferred substrate comprises4-chloro-ortho-xylene, optionally in combination with at least one of3-chloro-ortho-xylene, ortho-xylene, or chlorotoluic acid.

The substrate comprising at least one halo-ortho-xylene is combined inthe reaction mixture with at least one solvent, which preferablycomprises a lower aliphatic carboxylic acid. Illustrative examples oflower aliphatic carboxylic acids employed in the process of the presentinvention, include, but are not limited to, acetic acid, propionic acid,butanoic acid, pentanoic acid, or hexanoic acid. Acetic acid ispreferred.

At least one metal catalyst is used in the present invention. The atleast one metal catalyst comprises a metal compound with a metalselected from the group consisting of cobalt, manganese, vanadium,copper, molybdenum, and iron, and mixtures thereof. Preferably, a metalcompound is a salt of the metal and more preferably an acetate oracetylacetonate of the metal. Illustrative metal compounds which aresuitable for use in the invention include, but are not limited to,cobalt dibromide hexahydrate, cobalt dichloride, cobalt (II) acetate,cobalt (II) acetylacetonate, cobalt (III) acetylacetonate, cobalt (II)hexafluoroacetylacetonate, cobalt (II) picolinate, manganese (III)acetate, manganese (II) acetate, manganese (II)hexafluoroacetylacetonate trihydrate, manganese (III) acetylacetonate,manganese (II) acetylacetonate, manganese dichloride tetrahydrate,manganese dibromide, manganese (II) picolinate, manganese (III)picolinate, manganese (III) bromide acetylacetonate, vanadyl (IV)acetate (VO[OC(O)CH₃]₂), vanadyl (IV) acetylacetonate, copper (I)acetate, molybdenyl (VI) acetylacetonate (MoO₂[C₅H₇O₂]), iron (II)acetate, and hydrates, and anhydrous compounds, and mixtures thereof.Preferred metal catalysts include mixtures of cobalt (II) bromidehexahydrate with either cobalt (II) picolinate, manganese (II) bromide,manganese (II) chloride tetrahydrate, manganese (III) bromideacetylacetonate, manganese (II) acetate, manganese (III) acetatedihydrate, manganese (II) acetylacetonate, manganese (III)acetylacetonate, or manganese (II) hexafluoroacetylacetonate trihydrate;mixtures of cobalt (II) acetate with manganese (III) acetate ormanganese (II) bromide; and ternary mixtures of cobalt (II) acetate withmanganese (III) acetate and manganese (II) bromide; or of cobalt (II)acetate with manganese (III) acetate and cobalt (II) bromide; or ofcobalt (II) acetate with manganese (III) acetate and iron (II) bromide;or of cobalt (II) acetate with manganese (III) acetate and either copper(I) bromide or copper (II) bromide.

The molar ratio of halo-ortho-xylene substrate to the at least one metalcatalyst is in a range of about 20-600:1, preferably in a range of about50-300:1, and most preferably in a range of about 80-250:1. Inespecially preferred embodiments the molar ratio of halo-ortho-xylenesubstrate to the at least one metal catalyst is about 200:1. The atleast one metal catalyst may be added in one portion to the substrate orin more than one portion during the course of the reaction.

An effective amount of at least one promoter may optionally be used inthe reaction mixture. The term “effective amount”, as used herein,includes that amount of promoter capable of either increasing (directlyor indirectly) the conversion of halo-ortho-xylene or increasingselectivity toward halo-phthalic acid or halo-phthalic anhydride.Optimum amounts of promoter can vary based on reaction conditions andthe identity of other constituents, yet can be readily determined inlight of the discrete circumstances of a given application. In typicalembodiments an effective amount of promoter may have a value in a rangebetween about 0.01 mole % and about 20 mole %, preferably between about0.1 mole % and about 12 mole %, and more preferably between about 0.4mole % and about 10 mole %, based on halo-ortho-xylene substrate.

Suitable organic promoters include, but are not limited to,

(i) imides such as phthalimide, 4-chloro-phthalimide,3-chloro-phthalimide, dichloro-phthalimide, N-hydroxyethylphthalimide,and N-hydroxymethylphthalimide;

(ii) N-hydroxy imides such as N-hydroxyphthalimide,4-chloro-N-hydroxyphthalimide, 3-chloro-N-hydroxyphthalimide,dichloro-N-hydroxyphthalimide, 4-bromo-N-hydroxyphthalimide,3-bromo-N-hydroxyphthalimide, dibromo-N-hydroxyphthalimide,N-hydroxymaleimide, and N-hydroxysuccinimide;

(iii) hydroxamic acids such as 2-carboxyethanehydroxamic acid,2-carboxyethenehydroxamic acid, and 2-carboxyphenylhydroxamic acids offormula I:

wherein each R is independently halogen, preferably chloro or bromo; oralkyl, and n is 0-4;

(iv) arylaldehydes such as substituted benzaldehydes of the formula(II):

wherein R¹ is alkyl and each R² is independently halogen, preferablychloro or bromo; or alkyl, and n is 0-4;

(v) onium halides such as ammonium halides and phosphonium halides,preferably chlorides or bromides;

(vi) guanidinium halides, preferably chlorides or bromides; and

(vii) alkali metal halides, preferably chlorides or bromides.

Preferred hydroxamic acids include, but are not limited to,unsubstituted 2-carboxyphenylhydroxamic acid,4-chloro-2-carboxyphenylhydroxamic acid,3-chloro-2-carboxyphenylhydroxamic acids, anddichloro-2-carboxyphenylhydroxamic acid. Preferred arylaldehydesinclude, but are not limited to, alkylchlorobenzaldehydes such as3-chloro-2-methylbenzaldehyde, 4-chloro-2-methylbenzaldehyde, anddichloro-2-methylbenzaldehyde. Preferred onium halides include, but arenot limited to, tetraalkylammonium bromides such as tetraethylammoniumbromide and tetrabutylammonium bromide. Preferred guanidinium halidesare hexaethylguanidinium chloride and hexaethylguanidinium bromide. Apreferred alkali metal halide is sodium bromide. Especially preferredpromoters are N-hydroxyphthalimide and 4-chloro-N-hydroxyphthalimide.

The term “alkyl” as used in the various embodiments of the presentinvention is intended to designate both normal alkyl, branched alkyl,aralkyl, and cycloalkyl radicals. Normal and branched alkyl radicals arepreferably those containing from 1 to about 12 carbon atoms, and includeas illustrative non-limiting examples methyl, ethyl, propyl, isopropyl,butyl, tertiary-butyl, pentyl, neopentyl, and hexyl. Cycloalkyl radicalsrepresented are preferably those containing from 3 to about 12 ringcarbon atoms. Some illustrative non-limiting examples of thesecycloalkyl radicals include cyclobutyl, cyclopentyl, cyclohexyl,methylcyclohexyl, and cycloheptyl. Preferred aralkyl radicals are thosecontaining from 7 to about 14 carbon atoms; these include, but are notlimited to, benzyl, phenylbutyl, phenylpropyl, and phenylethyl.

The oxygen source used in the present invention may be high purityoxygen or molecular oxygen, air, oxygen-enriched air, or oxygen dilutedwith another gas which has no negative effects on the reaction, such asnitrogen, noble gases, argon. The concentration of diluent gas, whenpresent, in the oxygen source may amount to about 1 to about 95 volume%, preferably about 5 to about 90 volume %, and more preferably about 10to about 80 volume %. In a preferred embodiment the oxygen source isoxygen-enriched air containing about 28 mole % oxygen.

Oxygen in the form of an oxygen source may be introduced into thereaction mixture by any convenient means. In one embodiment the reactionmixture is agitated or stirred under a positive pressure of oxygensource. A preferred pressure is in a range of between about 1300 andabout 8300 kilopascals. A more preferred pressure is in a range ofbetween about 3400 and about 7100 kilopascals. In an especiallypreferred embodiment the pressure is about 6900 kilopascals.

The reaction mixture is heated to a temperature effective to promoteoxidation of at least one of and preferably both methyl groups ofhalo-ortho-xylene in the presence of the at least one catalyst andoxygen source. Preferably the reaction mixture is heated to atemperature in a range of between about 80° C. and either thetemperature at which either catalyst or promoter is no longer effectivefor promoting reaction or the effective boiling point of the reactionmixture under the prevailing pressure, whichever of the two is the lowertemperature. More preferably the reaction mixture is heated to atemperature in a range of between about 100° C. and about 230° C. andmost preferably in a range of between about 110° C. and about 150° C. atthe prevailing pressure.

The products of the oxidation reaction comprise those obtained byoxidation of at least one of and preferably both the two aromatic methylgroups. In particular the products comprise halotoluic acid andhalophthalic acid, respectively. Halophthalic anhydride may also bepresent depending upon the reaction conditions. It is to be understoodthat product mixtures comprising halophthalic acid may comprise up to100% halophthalic anhydride assuming all the halophthalic acid hasdehydrated. In a preferred embodiment the substrate halo-ortho-xylenecomprises 4-chloro-ortho-xylene and the products comprise chlorotoluicacid and 4-chlorophthalic acid, optionally with 4-chlorophthalicanhydride. In another preferred embodiment the substratechloro-ortho-xylene comprises a mixture of 3-chloro- and4-chloro-ortho-xylene and the products comprise chlorotoluic acids and amixture of 3-chloro- and 4-chlorophthalic acid optionally with 3-chloro-and 4-chlorophthalic anhydride. When ortho-xylene is present in thesubstrate, then a small amount of toluic acid and phthalic acid(optionally with phthalic anhydride) may also be obtained in addition tothe oxidation products of halo-ortho-xylene.

The product halophthalic anhydrides (or halophthalic acids which may beconverted to halophthalic anhydrides) may be used in processes to makevarious types of aromatic polyethers, particularly polyetherimides. Inone embodiment a product comprising 4-chlorophthalic anhydride (or amixture thereof with 3-chlorophthalic anhydride) may be reacted with atleast one diamine to prepare bis(chlorophthalimide) compounds which canserve as monomer for polyetherimide synthesis. For example,polyetherimides are conveniently prepared by the reaction of salts ofdihydroxyaromatic compounds, such as a bisphenol A disodium salt, withbis(halophthalimides) as illustrated by1,3-bis[N-(4-chlorophthalimido)]benzene, which has the structure

According to U.S. Pat. Nos. 5,229,482 and 5,830,974, the preparation ofaromatic polyethers may be conducted in solution in relatively non-polarsolvents, using a phase transfer catalyst which is substantially stableunder the temperature conditions employed. Solvents disclosed in U.S.Pat. No. 5,229,482 include o-dichlorobenzene, dichlorotoluene,1,2,4-trichlorobenzene and diphenyl sulfone. In U.S. Pat. No. 5,830,974,monoalkoxybenzenes such as anisole, diphenylether, or phenetole areemployed. Solvents of the same types may be used for the preparation ofbis(halophthalimide) intermediates, particularly bis(chlorophthalimide)intermediates, for polyetherimides.

The reaction of diamine with 4-halophthalic anhydride (or a mixturethereof with 3-halophthalic anhydride) in the presence of any phthalicanhydride arising from ortho-xylene oxidation may produce trace amountsof the mono-halo species. For example the reaction of diamine with4-chlorophthalic anhydride (or a mixture thereof with 3-chlorophthalicanhydride) in the presence of any phthalic anhydride arising fromortho-xylene oxidation may produce trace amounts of the mono-halospecies, 1-N-(4-chlorophthalimido)-3-N-(phthalimido)benzene in additionto 1,3-bis[N-(4-chlorophthalimido)]benzene (optionally in the presenceof 3-chloro species). The mono-halo species may serve as a chain-stopperin reaction with salts of dihydroxyaromatic compounds in polyetherimidesynthesis.

The process of the present invention may be performed in batch mode oras a semi-continuous or continuous process. In one embodiment theproducts of the oxidation reaction may be isolated by conventionalmeans, such as one or more steps of distillation or extraction. Inanother embodiment the products are at least partially recycled into afurther oxidation process to increase conversion of halo-ortho-xylene orto increase conversion of halo-toluic acid, or both.

Embodiments of the invention are illustrated by the followingnon-limiting examples. When amounts are specified, they apply to theoriginally incorporated components rather than those remaining after anyreaction. Analytical samples were quenched withbis(trimethylsilyl)trifluoroacetamide, diluted with tetrahydrofuran, andanalyzed by gas chromatography versus an internal standard. Samplecomponent concentrations, including remaining halo-ortho-xylene startingmaterial, were determined using response factors that were measuredusing authentic compounds. Although results are reported forchlorophthalic acid, it is to be understood that the sample may havecontained at least some chlorophthalic anhydride before quenching andderivatization.

EXAMPLES 1-34

Oxidation reactions were performed at 100° C. and 3447 kilopascals using28% oxygen-enriched air and 2 molar ortho-chloro-xylene (referred tohereinafter as “4ClOX”) in glacial acetic acid in the presence of 0.5mole % cobalt (II) acetate hexahydrate and 0.5 mole % manganese (III)acetate dihydrate, both based on ortho-chloro-xylene. Differentpromoters were included in the reaction mixture at either 1 mole % or 10mole % based on ortho-chloro-xylene. The promoters used wereN-hydroxyphthalimide (hereinafter referred to as NHPI),4-chloro-N-hydroxyphthalimide (4ClNHPI), N-hydroxymaleimide (NHMI),N-hydroxysuccinimide (NHSI), phthalimide (PI), N-hydroxyethylphthalimide(NHEPI), and N-hydroxymethylphthalimide (NHMPI),2-carboxyphenylhydroxamic acid of formula I (CPHA), and4-chloro-2-methylbenzaldehyde (4CMB). The reactions were run for 100minutes before sampling. Duplicate reactions were run in every case. Acontrol reaction run for 60 minutes under the same conditions exceptwithout added promoter and using 5 molar concentration of 4ClOX gave nodetectable amounts of diacid. Analytical results are shown in Table 1.

TABLE 1 Example Promoter (mole %) 4ClOX Conversion % Yield Diacid  1NHPI (10) 100 24.6  2 NHPI (10) 100 30.9  3 4ClNHPI (10) 100 35.8  44ClNHPI (10) 100 35.3  5 NHSI (10) 100 40.3  6 NHSI (10) 100 41.3  7NHMI (10) 100  5.1  8 NHMI (10) 100  5.3  9 NHEPI (10) 89.9  4.2 10NHEPI (10) 90.5  4.4 11 NHMPI (10) 91.8  5.3 12 NHMPI (10) 96.3  8.5 13PI (10) 98.5  9.8 14 PI (10) 96.2  7.1 15 CPHA (10) 97.6 23.3 16 CPHA(10) 100 25.4 17 NHPI (1) 100 32.1 18 NHPI (1) 100 33.5 19 4ClNHPI (1)100 32.8 20 4ClNHPI (1) 100 38.8 21 NHSI (1) 100 30.5 22 NHSI (1) 10030.4 23 NHMI (1) 97.4 14.1 24 NHMI (1) 97.8 16.0 25 NHEPI (1) 97.7 14.226 NHEPI (1) 100 15.7 27 NHMPI (1) 100 15.3 28 NHMPI (1) 100 16.0 29 PI(1) 98.5 14.6 30 PI (1) 100 15.3 31 CPHA (1) 98.6 21.7 32 CPHA (1) 98.026.6 33 4CMB (1) 100  32.4* 34 4CMB (1) 100  38.4* *corrected for anyproduct arising from oxidation of promoter

EXAMPLES 35-76

Oxidation reactions were performed at 150° C. and 3447 kilopascals using28% oxygen-enriched air and 2 molar 4ClOX in glacial acetic acid in thepresence of 0.5 mole % cobalt source and 0.5 mole % manganese source,both based on ortho-chloro-xylene. Temperature and pressure werecontrolled to remain relatively constant throughout the reaction. Thepromoter NHPI was included in the reaction mixture at 1 mole % based onortho-chloro-xylene. The reactions were run for 120 minutes beforesampling. The catalyst sources used were manganese (III) acetate,manganese (II) acetate, manganese (II) hexafluoroacetylacetonatetrihydrate, manganese (III) acetylacetonate, manganese (II)acetylacetonate, manganese dichloride tetrahydrate, manganese dibromide,cobalt dibromide hexahydrate, cobalt dichloride, cobalt (II) acetate,cobalt (II) acetylacetonate, cobalt (III) acetylacetonate, and cobalt(II) hexafluoroacetylacetonate. Duplicate reactions were run in everycase. Analytical results are shown in Table 2. The catalyst combinationsof manganese (II) acetate with cobalt (II) acetate; cobalt (II)acetylacetonate; cobalt (III) acetylacetonate; and cobalt (II)hexafluoroacetylacetonate gave greater than 80% conversion of 4ClOX inthe presence of promoter but no detectable amounts of diacid oxidationproducts under these conditions.

TABLE 2 Exam- Manganese Cobalt Promoter 4CIOX % Yield ple source sourcemole % Conversion Diacid 35 (acetate)3 dibromide none 100 100 36(acetate)3 dibromide none 100 100 37 (acetate)3 dibromide 1 100 100 38(acetate)3 dibromide 1 100 100 39 (acetate)3 dichloride none 65.4 0 40(acetate)3 dichloride none 59.9 0 41 (acetate)3 dichloride 1 94.3 5.2 42(acetate)3 dichloride 1 100 24.1 43 (acetate)3 (acetate)2 none 15.1 0 44(acetate)3 (acetate)2 none 12.2 0 45 (acetate)3 (acetate)2 1 94.6 3.0 46(acetate)3 (acetate)2 1 96.8 0 47 (acetate)3 (acac)2 none 28.9 0 48(acetate)3 (acac)2 none 19.6 0 49 (acetate)3 (acac)2 1 94.3 5.2 50(acetate)3 (acac)2 1 100 24.1 51 (acetate)3 (HF-acac)2 1 83.0 0 52(acetate)3 (HF-acac)2 1 83.8 4.3 53 (acetate)2 dibromide none 100 100 54(acetate)2 dibromide none 100 100 55 (acetate)2 dibromide 1 100 100 56(acetate)2 dibromide 1 100 100 57 (acetate)2 dichloride none 54.2 0 58(acetate)2 dichloride none 56.4 0 59 (acetate)2 dichloride 1 95.0 12.960 (acetate)2 dichloride 1 95.9 11.0 61 (HF-acac)2 dibromide 1 100 10062 (HF-acac)2 dibromide 1 100 100 63 (acac)2 dibromide 1 100 100 64(acac)2 dibromide 1 100 100 65 (acac)3 dibromide 1 100 100 66 (acac)3dibromide 1 100 100 67 dichloride dibromide 1 100 100 68 dichloridedibromide 1 100 100 69 dibromide dibromide 1 100 100 70 dibromidedibromide 1 100 100 71 (acetate)3 dibromide 1 100 100 72 (acetate)3dibromide 1 100 100  73* (picolinate)2 dibromide none 100 50.1  74*(picolinate)3 dibromide none 100 22.9  75* Br(acac)2 dibromide none 100100  76* none dibromide + none 100 34.2 (picolinate)2 *sample taken at60 minutes

EXAMPLES 77-83

Oxidation reactions were performed at 150° C. and 3447 kilopascals using28% oxygen-enriched air and 2 molar 4ClOX in glacial acetic acid in thepresence of 0.5 mole % cobalt source or of manganese source or of each,both based on ortho-chloro-xylene. Various promoters were included inthe reaction mixture at 0.5 mole % based on ortho-chloro-xylene. Thepromoters used were tetraethylammonium bromide, tetrabutylammoniumbromide, and sodium bromide. Temperature and pressure were controlled toremain relatively constant throughout the reaction. The reactions wererun for 60 minutes before sampling. Analytical results are shown inTable 3.

TABLE 3 Manganese Cobalt 4ClOX % Yield Example source source PromoterConversion Diacid 77 (acetate)3 (acetate)2 none 0 0 78 (acetate)3 noneNaBr 6.7 0 79 (acetate)3 (acetate)2 NaBr 100 100 80 (acetate)3 none TEAB12.4 0 81 (acetate)3 (acetate)2 TEAB 100 87.6 82 (acetate)3 none TBAB10.6 0 83 (acetate)3 (acetate)2 TBAB 100 95.5

EXAMPLES 84-93

Oxidation reactions were performed at 150° C. and 3447 kilopascals using28% oxygen-enriched air and 2 molar 4ClOX in glacial acetic acid in thepresence of 0.5 mole % cobalt source or of manganese source or of each,both based on ortho-chloro-xylene. A third metal compound was includedin the reaction mixture at 0.5 mole % based on ortho-chloro-xylene. Thethird metal compounds used were iron (II) bromide, iron (II) chloride,manganese (II) bromide, manganese (II) chloride, cobalt (II) chloride,cobalt (II) bromide, copper (I) bromide, and copper (II) bromide.Temperature and pressure were controlled to remain relatively constantthroughout the reaction. The reactions were run for 60 minutes beforesampling. Promoters and analytical results are shown in Table 4.

TABLE 4 Manganese Cobalt 3d metal 4ClOX % Yield Example source sourcecompound Conversion Diacid 84 (acetate)3 none FeBr2 11.5 0 85 (acetate)3none MnBr2 26.5 0 86 (acetate)3 (acetate)2 FeCl2 14.9 0 87 (acetate)3(acetate)2 MnBr2 100 95.0 88 (acetate)3 (acetate)2 MnCl2 42.0 0 89(acetate)3 (acetate)2 FeBr2 100 64.6 90 (acetate)3 (acetate)2 CoCl2 84.16.9 91 (acetate)3 (acetate)2 CoBr2 100 100 92 (acetate)3 (acetate)2 CuBr89.2 9.1 93 (acetate)3 (acetate)2 CuBr2 81.6 6.2

While typical embodiments have been set forth for the purpose ofillustration, the foregoing descriptions and examples should not bedeemed to be a limitation on the scope of the invention. Accordingly,various modifications, adaptations, and alternatives may occur to oneskilled in the art without departing from the spirit and scope of thepresent invention.

What is claimed is:
 1. A method for oxidizing a substrate comprising atleast one halo-ortho-xylene which comprises combining the substrate in asolvent with at least one metal catalyst and heating in the presence ofan oxygen source to produce a product comprising halo-ortho-phthalicacid or halo-ortho-phthalic anhydride.
 2. The method of claim 1 whereinthe substrate comprises chloro-ortho-xylene or fluoro-ortho-xylene. 3.The method of claim 1 wherein the substrate further comprises at leastone halo-toluic acid.
 4. The method of claim 3 wherein the halo-toluicacid comprises at least one chlorotoluic acid.
 5. The method of claim 1wherein the solvent comprises acetic acid.
 6. The method of claim 1wherein the at least one metal catalyst comprises at least one compoundof cobalt.
 7. The method of claim 6 wherein the at least one metalcatalyst further comprises at least one metal compound containing ametal selected from the group consisting of manganese, iron, copper,vanadium, and molybdenum.
 8. The method of claim 7 in which the molarratio of halo-ortho-xylene substrate to the at least one metal catalystis in a range of about 20-600:1.
 9. The method of claim 6 wherein thereaction mixture further comprises an effective amount of at least onepromoter selected from the group consisting of (i) phthalimide,4-chloro-phthalimide, 3-chloro-phthalimide, dichloro-phthalimide,N-hydroxyethylphthalimide, N-hydroxymethylphthalimide; (ii)N-hydroxyphthalimide, 4-chloro-N-hydroxyphthalimide,3-chloro-N-hydroxyphthalimide, dichloro-N-hydroxyphthalimide,4-bromo-N-hydroxyphthalimide, 3-bromo-N-hydroxyphthalimide,dibromo-N-hydroxyphthalimide, N-hydroxymaleimide, N-hydroxysuccinimide;(iii) 2-carboxyethanehydroxamic acid, 2-carboxyethenehydroxamic acid,2-carboxyphenylhydroxamic acids of formula I:

wherein each R is independently halogen, chloro or bromo; or alkyl, andn is 0-4; (iv) substituted benzaldehydes of the formula (II):

wherein R¹ is alkyl and each R² is independently halogen, chloro orbromo; or alkyl, and n is 0-4; (v) ammonium halides, ammonium chlorides,ammonium bromides, phosphonium halides, phosphonium chlorides,phosphonium bromides; (vi) guanidinium halides, guanidinium chlorides,guanidinium bromides; and (vii) alkali metal halides, alkali metalchlorides, and alkali metal bromides.
 10. The method of claim 1 in whichthe reaction mixture is heated to a temperature in a range of betweenabout 100° C. and about 230° C. at pressure in a range of between about1300 and about 8300 kilopascals.
 11. The method of claim 1 wherein theproduct mixture comprises halo-phthalic acid or halo-phthalic anhydride.12. A method for oxidizing a substrate comprising 4-chloro-ortho-xylenewhich comprises combining chloro-ortho-xylene in acetic acid solventwith at least one metal catalyst which is a metal compound comprisingcobalt, and heating in the presence of an oxygen source to produce aproduct comprising 4-chlorophthalic acid or 4-chlorophthalic anhydride.13. The method of claim 12 wherein the substrate further comprises3-chloro-ortho-xylene.
 14. The method of claim 12 wherein the substratefurther comprises chlorotoluic acid.
 15. The method of claim 12 whereinthe substrate further comprises both 3-chloro-ortho-xylene andchlorotoluic acid.
 16. The method of claim 12 wherein the at least onemetal catalyst further comprises at least one metal compound containinga metal selected from the group consisting of manganese, iron, andcopper.
 17. The method of claim 12 in which the molar ratio of4-chloro-ortho-xylene substrate to the at least one metal catalyst is ina range of about 50-300:1.
 18. The method of claim 12 wherein thereaction mixture further comprises an effective amount of at least onepromoter selected from the group consisting of (i) phthalimide,4-chloro-phthalimide, 3-chloro-phthalimide, dichloro-phthalimide; (ii)N-hydroxyphthalimide, 4-chloro-N-hydroxyphthalimide,3-chloro-N-hydroxyphthalimide, dichloro-N-hydroxyphthalimide,4-bromo-N-hydroxyphthalimide, 3-bromo-N-hydroxyphthalimide,dibromo-N-hydroxyphthalimide, N-hydroxymaleimide, N-hydroxysuccinimide;(iii) 2-carboxyphenylhydroxamic acids of formula I:

wherein each R is independently halogen, chloro or bromo; or alkyl, andn is 0-4; (iv) substituted benzaldehydes of the formula (II):

wherein R¹ is alkyl and each R² is independently halogen, chloro orbromo; or alkyl, and n is 0-4; (v) ammonium halides, ammonium chlorides,ammonium bromides, (vii) alkali metal halides, alkali metal chlorides,and alkali metal bromides.
 19. The method of claim 12 in which thereaction mixture is heated to a temperature in a range of between about100° C. and about 230° C. at pressure in a range of between about 1300and about 8300 kilopascals.
 20. A method for producing a product mixturecomprising 4-chlorophthalic acid or 4-chlorophthalic anhydride whichcomprises oxidizing a substrate comprising 4-chloro-ortho-xylene,optionally in the presence of chlorotoluic acid, which comprises thesteps of (i) combining substrate in acetic acid solvent with at leastone metal catalyst comprising cobalt, and optionally manganese, andheating in the presence of an oxygen source to a temperature in a rangeof between about 100° C. and about 230° C. at pressure in a range ofbetween about 1300 and about 8300 kilopascals, wherein the molar ratioof substrate to the at least one metal catalyst is in a range of about80-250:1; and (ii) isolating product comprising 4-chlorophthalic acid or4-chlorophthalic anhydride.
 21. The method of claim 20 wherein thesubstrate further comprises 3-chloro-ortho-xylene.
 22. The method ofclaim 20 wherein the reaction mixture further comprises an effectiveamount of at least one promoter selected from the group consisting ofN-hydroxyphthalimide, 4-chloro-N-hydroxyphthalimide,3-chloro-N-hydroxy-phthalimide, N-hydroxymaleimide,N-hydroxysuccinimide, 2-carboxyphenylhydroxamic acid,4-chloro-2-methylbenzaldehyde, tetraethylammonium bromide,tetrabutylammonium bromide, and sodium bromide.